Colloids and Surfaces, 60 (1991) 127-144 127

Elsevier Science Publishers B-V., Amsterdam

Characte,rization of the wettability of solid particles by

film flotation
1. Experimental investigation

D-W. Fuerstenau, Jianli Ciao and MC. Williams

Department of Materials Science and Miner& Engineerhg, University of California,
Berkeley, CA 94720, USA
(Received 17 December 1990; accepted 22 April 1991)

Abstract

Film flotation is a technique that can be used for assessing the wetting characteristics
of particulates. In film flotation, particles placed onto the surface of a liquid are imbibed
into the liquid only when their critical wettin surface tenSicJn is equal to or higher
than the surface tension of the wetting liquid. The efficacy of the method is demon-
strated by film floating homogeneous and hydrophobic particles of sulfur, silver iodide,
methylated glass beads and quartz, paraffin wax-coated coal and surfactant-coated
pyrite. Other factors such as particle size, particle density, film flotation time and the
nature of the wetting liquid have a negligible effect on the results of fiIm flotation
in the range of conditions tested. Film flotation is sensitive mainly to the surface
hydrophobicity and the heterogeneity of particles.

INTRODUCTION

The wettability of solid particles is known to be an important par-

ameter that influences many technological processes such as froth
flotation, oil agglomeration, solid-liquid separation and dust abate-
ment. The wettability of a solid is often represented by its critical
wetting surface tension (yc), which was defined by Zisman [l] as the
surface tension of a liquid which just forms a zero contact angle on
the solid.
The critical wetting surface tension. is commonly determined from
the well-known Z&man plot based on the contact angle measurements
[l].Several other methods such as advancing solidificaticn front, adhe-
sion, sedimentation volume and immersion time have been used to
assess this parameter [Z-5]. Although such methods have been success-
ful for assessing the wettability of homogeneous materials such as
polymers, each of these methods has its specific difficulties either in
carrying cut the experimental measurement or in the interpretation of

0166-6622/91/$03.50 0 1991 Elsevier Science Publishers B.V. All rights resermd.

128

the results when dealing with heterogeneous particles such as coals

[6,7]. Furthermore, most of these methods can only assess the average
wetting properties of either bulk or particulate samples.
Since the surfaces of most particles exhibit marked heterogeneity
because of differences in chemical composition andlor crystalline orien.
tation, an assembly of fine particles may h a v e widely differinB surface
properties. In response to the need for a technique which allows charac-
terization of the distribution of these properti~ within a particulate
assembly,, a film flotation technique was recently devised in our
laboratories [6-10], The application of film flotation for the character-
ization of coal powders has proved to be extremely ~ because it
gives information on the distribution of wetting characteristics and
degree of surface heterogeneity of the coal particles, and offers a means
for correlating surface properties with particle behavior in surface~
baaed processes [11-14]. A similar experimental technique was also
developed independently by M a r m u r et al. |151, but they only presented
the results in terms of the total sinking concentration (or surface
tension) TSC and total floating concentration TFC. Ramesh and
Somasundaran [16], and Mohal and C h a n d e r [17l have also proposed
new ways to assess the wettability of particulates; Ramesh and
Somasundaran by centrifugally sinking particles that had been placed
on the surface of the liquid, and Mohal and Chander by determining
the immersion time of individual coal particles using a high speed
camera. Hornsby and Leja [18], and Yarar and Kaoma [19] reported
using flotation response in m e t h a n o l - w a t e r solutions of p r o ~ i v e l y
decreasing surface tension to characterize the relative wettability and
flotability.
l~acesses related to film flotation have been proposed for making
mineral separations. For example. Varbanov et al. [20] have published
papers to describe a process, which they term static flotation, wherein
a thin layer of preaerated particles flow onto a quiescent bath of water.
The water-wet particles sink and the hydrophobic particles float and
al~ skimmed off. Our technique, however, uses dry particles and a
range of surface tensions in order to measure wetting surface tensions.
This paper presents the results of extensive experimental investiga-
tion of the film flotation technique for c h m c t e r i m n g Me hydrophohic/
hydl~philic nature of an assembly of particles, including both homo-
geneous and hetel~geneous materials. From these meast,,-ements, the
effects of such variables as surface h.~lrophobicity, sturfa~ homo-
geneity, particle size and particle density on film flotation response
were delineated. Contact angle measurements were used to assess the
wettability of homogeneous bulk material for comparison with the film
flotation response of particulates of t~he same materials. A theoretical
analysis of this technique is given in our companion paper [21].
MATERIALS AND METHODS

Materials used in this investigation were Cambria No. 78 bitumi-

nous and Dave Johnston subbituminous coals, Ceylon graphite (99.0%
carbon), sulfur (Nevada), quartz (Brazil), pyrite (Arizona) and Super-
brite glass beads (manufactured by Minnesota Mining and Manu-
facturing Co., Reflective Products Division). The monosized fractions
of coal, graphite, sulfur, quartz and pyrite were prepared by grinding
the samples in a small ceramic mill to avoid iron contamination and
then sieving the material with Tyler sieves. All chemicals used in this
study were reagent grade. Triply-distilled water was used throughout
the e.xperiments.
Glass beads and quartz particles were cleaned with hot concentrated
hydrochloric acid in order to remove impurities, specifically ferric ions.
The leached samples were rinsed repeatedly with triply-distilled water
until the conductivity of the supernatant remained constant. These
materials were then dried in an oven at 40°C for 36 h, and finally stored
in air-tight glass bottles. To make the surface of these particles homo-
geneously hydrophobic, 20 g of particles were reacted with 20 ml of
pure trimethylchlorosilane (TMCS) by agitating the suspension for two
hours at room temperature. Subsequently, the methylated particles
were washed three times with pure cyclohexane, dried in an oven at
110"C for 24 h, and then stored in a desiccator over silica gel to prevent
moisture adsorption.
Other materials were made hydrophobic by coating them with paraf-
fin wax using a simple vapor deposition procedure. To accbmplish this,
the vapor generated by heating paraffin wax was passed through a bed
of particles (1.5 g) by applying vacuum. To achieve a more uniform wax
coating on all particles, the bed was tumbled at least every 15 min. In
order to prepare surfaces having various degrees of hydrophobicity,
the coating process was carried out for 0.5, 3 and 8 h, after which the
wax-coated samples were stored in air-tight glass bottles. In the case
of pyrite, particles having different degrees of hydrophobicity were
prepared by mixing 3 g of 106 x 150 pm particles with 100 ml of solution
containing either 1 lo'-'or 5 10V4 1M potassium amyl xanthate (the
l l

,most common class of collector used in sulfide mineral flotation) at

pH 9 in a glass bottle and conditioning the suspension in a laboratory
shaker for 3 h at 25” C under nitrogen gas. The samples were then
filtered and dried under vacuum for 18 h at 25°C. A blank was run to
determine the wetting behavior of pyrite in the absence of xanthate.
The captive-bubble method was used to measure the contact angles
on methylated quartz and paraffin wax. To prepare a smooth surface,
a quartz specimen was first polished with sandpaper and then with
130

0.3 pm alumina powders on a polishing wheel. Subsequently, the

polished specimen was washed with triply-distilled water in an ultra-
sonic bath to remove any traces of polishing powder. After drying, the
polished specimen was methylated by the procedure discussed in the
foregoing paragraphs. The paraffin wax surface was prepared by pour-
ing molten paraffin into a dish and placing a polished glass plate over
it. Removal of the glass after the wax had solidified left a smooth
sutiface on the paraffin.
The sessile-drop method was used to measure contact angles on the
surface of a sulfur pellet, which hzd been prepared by pressing
106 x 150 pm sulfur particles in a 1.27 cm diameter mold for 10 min at
62 500 p.s.i. Contact angles were measured with a Ram&-Hart gon-
iometer using aqueous methanol solutions after either a bub’ole or a
liquid drop had contacted the surface of the specimen for about 5 min
in the case of the captive-bubble experiment or 0.5 min in the case of
the sessile-drop system. Each reading was an average of the angles
measured on both sides of the bubble in order to account for any slight
specimen tilt. The reported contact angles are the average of at least
four such readings, which varied within a range of t3”.
Film flotation experiments were performed by placing about 0.2-0.3 g
of closely sized particles (generally 106 x 150 pm) onto the surface of
the liquid in a single container cf radius 5 cm and depth I cm. By
having a conical bottom on the cylinder and a stopcock on the drain,
the particles that sink can readily be separated from those that float.
Depending on the wetting characteristics of the material and the sur-
face tension of the liquid used the particles either remain at the liquid/
vapor interface or are immediately engulfed by the liquid. Subse-
quently, the lyophobic (not imbibed) and lyophilic (imbibed) fractions
are recovered, dried and weighed. Unless otherwise specified, all film
flotation experiments in this investigation were carried out using
106 x 150 pm particles and aqueous methanol solutions as the wetting
liquid in a 20°C constant-temperature room. To delineate if there are
any effects of the heteropolar organic compounds used to regulate
surface tensions, one series of experiments was also carried sut with
aqueous solutions of ethanol, propanol, tertiary butanol, and acetone.

RESULTS AND DISCUSSION

Effect of .heterogeneity on nettability parameters

Because of differences in chemical composition and/or in crystal

orientation, fine particles in an assembly generally exhibit marked
heterogeneity and may have widely differing surface properties.
 131

Initially, the results of the film flotation response of very heterogeneous

materials (coal) will be presented to illustrate the distributed nature
of the surface of coal particles, which results from the distribution of
mineral matter in the coal and the distribution of surface oxygen
functional groups on the carbonaceous matrix. Figure 1 gives the cumu-
lative weight percent of Cambria No. 78 coal particles which refer to
the lyophobic (hydrophobic) fraction in film flotation as a function of
the surface tension of the test solution. As will be discussed in detail
[Zlf, in the absence of gravitational effects, a particle transfers sponta-
neously from the interface into the liquid phase just when the contact
angle becomes zero, that is when the film of liquid can spread over the
entire particle. (In actuality, to overcome gravitational effects, tl--2
contact angle must be just slightly greater than zero to prevent the
particles from sinkin g into the liquid.) Therefore, at any point along
the curve in Fig. 1, the particles that just sink have their individual
values of the critical wetting surface tensions that are equal to the
surface tension of the wetting liquid used in film flotation. Figure 2
presents the frequency distribution of critical wetting surface tensions
for Cambria No. 78 coal. These figures clearly show that heterogeneous
materials such as coal indeed exhibit a distribution of surface energies.

CRITICAL WElTING SURFACE TENSION OF PARTICLES, mN/m

0 20 40 60 80
E
2
3
100

80-
I
1
CAMaRIA
iO6X350
I
NO. 78
pm
COAL
1 II
I
1
I
1
I
I
0 I
E
’ I
I
8 60- I

2 __--_-__--------

5
w 40- I
kz I
I
K

9 20-

5
‘s
I ” I
=
r, o-
-0 20 40 60 80
SURFACE TENSION OF METHANOL SOLUTION, mN/m

Fig. 1. The cumulative percentage of lyophobic (hydrophobic) Cambria No. 78 coal

particles as a function of their wetting surface tension, as obtained from film flotation
with aqueous methanol solutions.
132

12
CAMBRIA NO. 78 COAL c
106X150 fit-n

-0 20 40 60 80
CRITICAL WEITING SURFACE TENSION OF PARTICLES, mN/m

Fig. 2. Frequency distribution of CambAa No. 78 coal particles as a function of their

critical wetting surface tension, as determined from film flotation with aqueous
methanol solutions.

Although the conventional methods commonly used to estimate the

wettability of powders provide only a single value for the critical
wetting surface tension of the material, irrespective of the hetero-
geneity of the solid, film flotation response curves can be used to
determine the distribution of wetting-related parameters [7,9,14]. Tne
critical wetting surface tension of the most hydrophobic particles in
the assembly, yyin, is the surface tension of the liquid at which none of
the particles remain (float) at the liquid surface (see Figs 1 and 2). The
critical wetting surface tension of the most hydrophilic particles in
the powder, JJ:““, is the surface tension of the liquid at which all the
particles remain at the liquid surface. The mean critical wetting surface
tension of all particles, ‘j;,, can be calculated from the film flotation
frequency distribution using the equation:

where 7;: is the critical surface tension of the particles and f(r,) is the
frequency distribution furrction. TCrepresents the mean wettability of
the assembly of particles. How 7, changes can be used as an index to
follow changes in the surface, caused by oxida.tion for example [12].
The standard deviation of the frequency distribution function, fly,,
 133

reflects the heterogeneity of the su: face and is given by

cry,
= 0.CL 112
-7,)2f(rc
1drc
[r 1 (2)

High oyc values correspond to more heterogeneous materials.

Effect of hydrophobicity and homogeneity of particZe surfaces

If the particles being investigated have a homogeneous surface, they

should exhibit a single critical wetting surface tension. In terms of
various 5ilm flotation parameters, this means that, for an ideal homo-
geneous surface, 7, = rp’” = JJ?“”= yc, and nyc= 0. Because all particles
should be imbibed into the liquid at surface tensions below 7, and none
imbibed above jjE, the film flotation par,tition curve must be virtually
vertical.
To test this hypothesis, the wetting behavior of a number of homo-
geneous and hydrophobic particles (TMCS-coated glass beads and
quartz, silver iodide and sulfur) was assessed using film flotation and
contact angle measurements with aqueous methanol solutions. As
expected, the acid-cleaned glass beads and quartz particles exhibited
hydrophilic surfaces, that is, they sink completely in triply-distilled
water. However, upon methylation, their surfaces should be covered
with a homogeneous layer of hydrophobic methyl groups 1221and their
film flotation curves should then be nearly vertical. Figure 3 presents
a plot of the cumulative percentage of methylated glass beads and
quartz particles that report to the float fraction as a function of the
critical wetting surface tension, along with a plot of the cosine of the
contact angles on the methylated quartz plate (Zisman plot). These
results clearly show that the three wetting parameters for these homo-
geneous, hydrophobic surfaces have almost the same value, namely
min -
Yc =5: Yc = Ycmnx=23mNm- ‘. This value is also in good agreement with
the critical wetting surface tension determined from the Zisman plot
(Fig. 3) using the contact angles measured on the methylated quartz
surface in the same aqueous methanol solutions. For a substrate
covered with a monolayer of methyl groups% values of 22-24 mN m-l
have been reported for yc [l]. Another conclusion drawn from these
results is that particle shape does not appear to affect the film flotation
response. The wetting tension distribution curves are identical even
though the shape of methylated spherical glass beads and quartz
particles is vastly different.
The film flotation results of crystalline silver iodide particles, which
are known to be hydrophobic, are presented in Fig. 4. Also, the contact
134

SURFACE TENSION OF Ml3HANOL SOLUTION. mN/m

\\

*1*t-
\*
TMCS-COATED
\ \
z c&A&BEADS

106X150 pm

- 0.0
-_-
40 60 80
CRITICAL WElTING SURFACE TENSION OF PARTICLES. mN/m

Fig. 3. Cumulative distribution of TMCS-coated glass beads and quartz particles as a

function of their critical wetting surface tensions as obtained by film flotation with
aqueous methanol solutions, and the cosine of the contact angle on TMCS-coated
quartz as a function of the solution surface tension.

angles measured on a pellet of the silver iodide using the sessile-drop

method reported by Fuerstenau and Gutsche [23] are reproduced in
Fig. 4. Since silver iodide particles crystallized from solution are quite
homogeneous, it is expected that the cumulative distribution curve
should be virtually vertical. The resu.lts given in this figure clearly
show that tb.e wetting parameters yrin, jjCand yr”” are almost identical
for tnis homogeneous sample and their values are in good agreement
with the value of yC determined from the Zisman plot on bulk material
(also Fig. 4).
Figure 5 presents the film flotation results of naturally hydrophobic,
homogeneous sulfur particles together with contact angles measured
on its compressed pellet using the sessile-drop method. The values of
rin and*?, for sulfur particles are 28.0 and 31.3 mN m- ’ respectively.
These values tire also in quite good agreement with the value of y
determined from the contact angle measurements (28.5 mN m-‘) in thz
present work and the reported yC values for sulfur (ranging from 27.5
to 31.5 mN m- 1) in the literature [19,24-261. A similar plot was reported
by Yarar and Kaoma [19] when plotting flotation recovery and cosine
 135

SURFACE TENSION OF METHANOL SOLUTION, mN/m

-- 0 20 40 60 80. n

~0 20 40 60 SO-‘-
CRITICAL WDllNG SURFACE TENSION OF PARTICLES, mN/m

Fig. 4. Cumulative distribution of silver iodide particles as a function of their critical

wetting surface tension as obtained by film flotation with aqueous methanol solutions,
and the cosine of the contact angle on a compressed pellet of silver iodide as a function
of the solution surface tension.

contact angle of sul.fur as a function of svurface tension of methanol

solution.
These studies of the wetting behavior of methylated glass beads and
quartz, silver iodide and sulfur using film flotation and contact angle
measurements confirm that particles transfer from the air/liquid inter-
face into the liquid phase (become lyophilic) when their critical wetting
surface tension is essentially equal to the surface tension of wetting
liquid used in film flotation. Table 1 summarizes the four wetting par-
ameters obtained from film flotation of methylated glass beads and
quartz, silver iodide, sulfur and Cambria No. 78 coal. As expected, the
values of 7, and bye of Cambria No. 78 coal are much higher than those
for the other materials, indicating that the coal particles are more
heterogeneous and hydrophilic than the other materials.
To confirm that the nature of the film flotation response of the coal
particles is indeed due to their heterogeneity, the particles were coated
to different degrees with paraffin wax. In this way, the particles being
tested have almost the same shape and density as those that were not
treated. In these experiments, .Cambria No. 78 coal particles were
coated with paraffin wax for either 0.5 or 3 h to prepare particles having
136

SURFACE TENSION OF Ml3-lANOL SOLUTION, mN/m

4
I
I SULFUR
o FILM FLOTATION

- 0.0
-0 20 40 60 SO---
CRITICAL WEITING SURFACE TENSION OF PARTICLES, mN/m

Fig. 5. Cumulative distribution of sulfur particles as a function of their critical wetting

surface tension as obtained by film flotation with aqueous methanol soluti’ons, and the
cosine of the contact angle on a compressed pellet of sulfur.

TABLE 1

Wetting parameters of 106 x 150 pm particles obtained from film flotation with aqueous
methanol solutions

min mnx
Material Yc YE 7, uye (II-IN m- ’ )

Methylated glass beads 22.5 23.5 23.0 0.3

Methylated quartz 22.5 23.5 23.0 0.3
Silver iodide 28.2 31.1 29.1 0.5
Sulfur 28.0 34.5 31.3 1.6
Cambria No. 78 coal 35.4 65.2 43.0 5.8

different degrees of hydrophobicity and surface homogeneity. Since the

longer the particles are coated with paraffin, the more hydrophobic
2nd homogeneous they should become, y, and cuC of the wax-coated
coal particles should decrease with increasing coating times. The film
flotation results are given in Fig. 6, along with the contact angles
(cosine) on paraffin wax at different surface tensions. From these re-
sults, one can indeed observe that the longer the coating time, the
more pronounced is the shift and steepness of the curves. These distri-
bution curves tend towards the limiting case corresponding to the
 137

SURFACE TENSlON OF METHANOL SOLUTION. mN/m

CAMBRIA NO. 78 COA

106X150 pm
o AS-RECEIVED
WAX-COATED FOR:

40 60
CRITICAL WEITING SURFACE TENSION OF PARTICLES, mN/m

Fig. 6. Cumulative critical wetting distribution curves of Cambria No. 78 coal particles
(as-received and wax-coated for 0.5 and 3 h) obtained by film flotation with aqueous
methanol solutions, and the cosine of the contact angle on paraffin wax.

vertical line at the critical wetting surface tension of parafin wax.

Since particles tend to stick together when they are coated excessively
with paraffin, this limiting case cannot be fully achieved by the vapor
coating method.
The four wetting parameters for as-received and wax-coated coal
particles are given in Table 2. The results show that 7, and o,~ of the
wax-coated sample decrease with increased coating time, indicating
that the coal particles have become more hydrophobic and homo-
geneous. Since the most lyophobic particles are expected to be those
that are totally covered by wax, J$“” of wax-coated samples should be

TABLE 2

Wetting parameters of 106 x 150 pm as-received and wax-coated Cambria No. 78

particles obtained from film Rotation with aqueous methanol solutions

Treatment y?‘” Yc
ma*
7, cy, (mN m- ’ )

As-received 35.4 65.2 43.0 5.8

Wax-coated for 0.5 h 23.5 40.0 30.4 3.2
Wax-coated for 3 h 22.4 29.7 25.3 1.6
138

the same as yC of paraffin wax. The value of 7:‘” (22.4 mN m- ‘) for

wax-coated coal is in good agreement with the value of yE for paraffin
wax determined in present work and with the value reported in the
literature [1,27-301.
A somewhat analogous experiment was perfry*med by studying the
film flotation response with pyrite that had been coated by an adsorbed
film of potassium amyl xanthate. Figure 7 presents the film flotation
results of pyrite particles with and without adsorbed potassium amyl
xanthate (K.AX). The four wetting parameters of pyrite that had under-
gone various treatmen+s are given in Table 3. One can see from the
results given in Fig. 7 and Table 3 that after adsorbing KAX, pyrite
particles are more hydrophobic and more homogeneous than untreated

60

PYRITE
106X150 pm
OOM

z 1

20
Jr/J I
40 60
I

80
CRITICAL WEITING SURFACE TENSION OF PARTICLES, mN/m

Fig. 7. Cumulative film flotation response curves for pyrite particles after adsorbing
potassium amyl xanthate from aqueous solutions at pH 9.

TABLE 3

Film flotation wetting parameters of 106 x 150 pm pyrite particles that had been
equilibrated with various amounts of potassium amyl xanthate c pH 9

Concentration (M) Yc
min
YC
ma*
7, cyc (mN m-l)

0 33.0 72.0 42.3 7.4

1.1o-5 30.0 60.0 39.6 5.4
5.10-4 27.5 44.0 32.0 2.6
 139

particles, and the more KAX adsorbed on the pyrite (at higher concen-
tration) the more hydrophobic and homogeneous are the particles.

Efectof particle clensity

Subsequently, we investigated the effect of particle density on film

flotation response. Figure 8 presents the results of film flotation experi-
ments with wax-coated graphite (specific gravity 2.2) and pyrite (spe-
cific gravity 5.0). The shape and the steepness of the curves for the
wax-coated samples are similar to each other. The values of r?‘” and yc
for both of these wax-coated samples are 22.5 mN m-l and 26.5 mN m- ‘.
These results indicate that particle density has little effect on the
results obtained by the film flotation of 106 x 150 urn particles.

Effect of particle size

The wetting characteristics of Cambria No. 78 coal. of various particle

sizes (53 x 75 urn, 75 x 106 pm, 106 x 150 pm, 150 x 212 pm, 212 x 300 urn
and 300 x 425 pm) were investigated to delineate the effect of particle
size on film flotation response. The results presented in Fig. 9 show
that, for all these size fractions, the partition curves are almost
identical, and indicate that yc does not significantly depend on particle

0 20 40 60 8;
CRITICAL WETTING SURFACE TENSION OF PARTICLES. mN/m

Fig. 8. The effect of particle density on the film Rotatioii response of wax-coated
graphite and pyrite in methanol solutions.
 CAMBRIA #78 COAi

s I

20
*
I

40
1

60 so
CRITICAL WIZITING SURFACE TENSION OF PARTICLES, mN/m

Fig. 9. The effect of particle size on the observed critical wetting surface tension
distribution of Cambria No. 78 coal obtained by film flotation with aqueous methanol
solutions.

size. For coal, the effect of gravitational forces is negligible over the
size range tested. Since particles smaller than 53 pm tend to aggregate,
this size range represents the lower size limit for which film fiotation
experiments can be conducted.

Effect of time

To ascertain if separation time has any effect on film flotation results,

a series of experiments was performed at times ranging from 1.5 to 50
min using graphite and Dave Johnston coal with aqueous methanol
solutions of 40.5 mM II-..-1 surface tension. Each point plotted in Fig. LO
is the average of three experiments and the error is within 5 percent.
As can be seen from the results given in this figure, the lyophobic
fraction obtained from film flotation is independent of the flotation
time.

Effect of the nature of the wetting liquidon film flotation

When using aqueous solutions of polar organic molecules to deter-

mine the wetting behavior of partially lyophobic solids, one is con-
cerned with effects of preferential adsorption of the organic species.
To test the possible effect of adsorption on film flotation response,
 141

‘r 40-
W

E SURFACE TENSION GO.5 mN/m

20 - 106X150 r;m
z 0 GRAPHITE
w 0 DAVE JOHNSTON COAL
3
I I I I I
Ol 2 5 10 2G 50 100
RETENTION TIME. minutes

Fig. 10. The effect of time on the film flotation response of graphite and Dave Johnston
coal particles with aqueous methanol solutions of 40.5 mN m-l.

graphite particles and Dave Johnston coal were film floated in aqueous
solutions made up with methanol, ethanol, propanol, tertiary butyl
alcohol and acetone. The results from these experiments are presented
in Figs 11 and 12, using surface tension data for these solutions from
the literature 17,311. Since all experimental data fall reasonably well
onto a single line for both materials, the effect of preferential adsorp-
tion of the organic species appears to be negligible for practical film
flotation. Using contact angle measurements, Zisman et al. [29,32] also
found that the value of y, of a solid is essentially the same when using
different aqueous solutions, although the values of the contact angles
may be different for solutions of surface tension higher than the critical
wetting surface tension.
In addition, an attempt was also made to estimate the wettability
parameters of coal using Fure organic liquids of different surface ten-
sions (as other investigators have done for determining the critical
wetting surface tension of low energy solids by contact angle measure-
ments). Liquids used for this purpose included o-xylene, carbon bi-
sulfide, monobromobenzene and aniI’ Ae. When film flotation ‘was
performed with these liquids, a discoloration of the liquid was noticed,
which indicates an interaction between the coal and the liquid. As a
result, reproducible and reliable partition curves could not be obtained.
It is important to note here that chemical interaction between the solid
 GRAPHITE
106X150 pm

z 20
o Ml3HANOL
q EWANOL
A PROPANOL
3 t i TEcREiLTANOL
5
2
z o. I

20
I

40
I

60 80
CRITICAL Wl3TtNG SURFACE TENSION OF PARTICLES. mN/m

Pig. 11. Film flotation response of graphite particles with various polar organic
soluticns.

DAVE JOHNSTON COAL

0 B 106X150 em
o METHANOL

20 -- 40 60 I 3
CRITICAL WEiTING SURFACE TENSION OF PARTICLES, mN/m

Fig. 12. Film flotation respcnse of Dave Johnston with various polar
organic solutions.
 143

and the liquid must be absent if film flotation is to give meaningful

results.

SUMMARY AND CONCLUSIONS

Film flotation is a technique developed in our laboratories that can

be used to assess the wetting characteristics of particulate samples
through determination -of the distribution of the critical wetting surface
tensi” of particles. The wetting parameters determined from the distri-
buti<. represent the statistical hydrophobicity and heterogeneity of
particles in the assembly.
The efficacy of this technique was confirmed by film floating homo-
geneous, hydrophobic particles of sulfur, silver iodide, methylated glass
beads and quartz, paraffin wax-coated coal and surfactant-coated pyrite,
and by measuring contact angles on these materials. The wetting
pal-ameters of highly homogeneous samples obtained from film flotation
are in good agre c~cni with the values of yc determined from contact
angle measurements. This indicates that particles in film flotation are
imbibed into the wetting liquid only when their critical wetting surface
tension is equal, to or higher than the surface tension of the wetting
liquid. Particle size, particle density, particle shape, film flotation time
and the nature of the wetting liquid were found to have a negligible
effect on the results of film flotation in the ranges tested. Film flotation
is sensitive mainly to the surface hydrophobicity and heterogeneity of
particles.

ACKNOWLEDGMENTS

The authors wish to acknowledge the U.S. Department of Energy,

Pittsburgh Energy Technology Center, Grant No. DE-FG22-84PC70776
and DE-FG22-86PC90507 for the support of this research.

REFERENCES

1 W.A. Zisman, Adv, Chem. Ser., 43 (1964) 1.

2 A.W. Neumann, E.I. Vargha-Butler, H.A. Hamza and D.R. Absolom, Colloids
Surfaces, 17 (1986) 131.
3 D.R. Absolom, K. Eom, E.I. Vargha-Butler, H.A. Hamza and A.W. Neumann,
CoIloids Surfaces, 17 (1986) 143.
4 E-1. Vargha-Butler, T-K. Zubovits, D.R. Absolom and A.W. Neumann, Chem.
Commun., 33 (1985) 255.
5 S. Gnrbsva, S. Contreras and J. Goldfarb, Colloid Polym. Sci., 256 (1978) 241.
6 D.W. Fuerstenau and M.C. Williams, Part. Charact., 4 (1987) 7.
144

7 J. Diao, Characterization of Wettability of Solid Particles by Film Flotation,

M.S. Thesis, University of California, Berkeley, 1987.
8 D.W. Fuerstenau, M-C. Williams and J. Diao, A Novel Technique for Assessing
Powder Lyophobicity/Lyophilicity, Paper presented at AIME Annual Meeting,
New Orleans, March 1986.
9 D.W. Fuerstenau and M-C. Williams, Colloids Surfaces, 22 (1987) 87.
10 M.C. Williams and D.W. Fuerstenau, Int. J. Miner. Process., 20 (1987) 153.
11 D-W. Fuerstenau, K.S. Narayanan, R.H. Urbina and J.L. Diao, in Moulijn (Ed.),
1987 International Conference on Coal Science, Elsevier, Amsterdam, 1587.
12 D.W. Fuerstenau, M.C. Williams, K.S. Narayanan, J.L. Diao and R.H. Urbina,
Energy Fuels, 2 (1988) 237.
13 D.W. Fuerstenau, J. Diao and J. Hanson, Characterization of Coal Particle
Surfaces by Film Flotation, Paper presented at American Chemical Society
National Meeting, Los Angeles, September 1988.
14 D.W. Fuerstenau, J. Diao and J. Hanson, Energy Fuels, 4 (1990) 34.
15 A. Marmur, W. Chen and G. Zografi, J. Colloid Interface Sci., 113 (1986) 114.
16 R. Ramesh and P. Somasundaran, J. Colloid Interface Sci., 139 (1990) 291.
17 B.R. Mohal and S. Chander, Colloids Surfaces, 21 (1986) 193.
18 D.T. Hornsby and J. Leja, Colloids Surfaces, 7 (1983) 339.
19 B. Yarar and J. Kaoma, Colloids Surfaces, 11 (1984) 429.
20 R. Varbanov, D. Nikolov, St. Balinova and B. Balinov, Trans. Inst. Min. Metall.
Sect. C: Mineral Process. Extr. Metall., 94 (1985) C125.
21 3. Diao and D.W. Fuerstenau, Colloids Surfaces, 60 (1991) 145.
22 J. Laskowski and J.A. Kitchener, J. Colloid Interface Sci., 29 (1969) 670.
23 D.W. Fuerstenau and Oliver Gutsche, The Flotation of Silver Iodide as a Model
Hydrophobic Mineral, Paper presented at AIME Annuai Meeting, Las Vegas,
February 1989.
24 S. Kelebek and G.W. Smith, Int. J. Min. Proc., 14 (1985) 275.
25 D.A. Olsen, R.W. Moravec and A.J. Osteraas, J. Phys. Chem., 7 (1967) 4464.
26 S. Kelebek, Surface Properties and Selective Flotation of Inherently Hydrophobic
Minerals, Ph.D. Thesis, McGill University, Montreal, Canada, 1984.
27 J.R. Dann, J. Colloid Interface Sci., 32 (1970) 302.
28 W-R. Gocd, J. Colloid Interface Sci., 44 (19’73) 63.
29 H-W. Fox and W.A. Zisman, J. Colloid Sci., 7 (1952) 428.
30 Von E. Wolfram, Kolloid Z. Z. Polym., 211 (1966) 84.
31 Handbook of Chemistry and Physics, 65th edn, CRC Press, Boca Raton, FL, 1985.
32 F. Schulman and W.A. Zisman, J. Colloid Sci., 7 (1952) 465.